P(NMe2)3介导1,2-二羰基化合物与α,β-不饱和酮的[1＋4]环化反应及多取代2,3-二氢呋喃的合成

doi:10.6023/cjoc202205021

有机化学 ›› 2022, Vol. 42 ›› Issue (11): 3805-3815.DOI: 10.6023/cjoc202205021 上一篇下一篇

研究论文

P(NMe₂)₃介导1,2-二羰基化合物与α,β-不饱和酮的[1＋4]环化反应及多取代2,3-二氢呋喃的合成

薛飞雪^a, 曾建伟^a, 严泰山^a, 韩杰^a^,^*(), 贺峥杰^a^,^b^,^*()

^a南开大学化学学院元素有机化学国家重点实验室天津 300071
^b天津化学化工协同创新中心天津 300071

收稿日期:2022-05-16 修回日期:2022-07-05 发布日期:2022-07-13
通讯作者: 韩杰, 贺峥杰
基金资助:
国家自然科学基金(21472096); 国家自然科学基金(22171143)

Synthesis of Polysubstituted 2,3-Dihydrofurans via P(NMe₂)₃- Mediated [1＋4] Annulation of 1,2-Dicarbonyl Compounds with α,β-Unsaturated Ketones

Feixue Xue^a, Jianwei Zeng^a, Taishan Yan^a, Jie Han^a(), Zhengjie He^a^,^b()

^aState Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071
^bCollaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071

Received:2022-05-16 Revised:2022-07-05 Published:2022-07-13
Contact: Jie Han, Zhengjie He
Supported by:
National Natural Science Foundation of China(21472096); National Natural Science Foundation of China(22171143)

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摘要/Abstract

在P(NMe₂)₃作用下, 1,2-二羰基化合物与α,β-不饱和酮顺利发生分子间[1＋4]环化反应, 生成带有全碳季碳中心的多取代2,3-二氢呋喃类化合物, 从而以较高的收率及较宽的底物范围提供了合成该类化合物的新方法. 在某些情况下, [1＋2]环化反应竞争发生生成多取代的环丙烷化合物. 借助密度泛函理论(DFT)计算手段, 讨论了反应机理及有关[1＋2]环化反应与[1＋4]环化反应的化学选择性.

关键词: 1＋4]环化反应, 1,2-二羰基化合物, [1＋2]环化反应, 2,3-二氢呋喃, Kukhtin-Remirez加合物

A [1＋4] annulation of 1,2-dicarbonyl compounds with α,β-unsaturated ketones has been readily realized under the mediation of P(NMe₂)₃, producing polysubstituted 2,3-dihydrofurans bearing a quaternary carbon center in fair to good yields with a broad substrate scope. This reaction accordingly constitutes a new synthetic method for such compounds. In some cases, a [1＋2] annulation reaction competitively occurs, delivering polysubstituted cyclopropanes. With the aid of density functional theory (DFT) calculation, a plausible mechanism for the [1＋4] annulation and the chemoselectivity between [1＋2] and [1＋4] annulations has been discussed.

Key words: 1＋4] annulation, 1,2-dicarbonyl compounds, [1＋2] annulation, 2,3-dihydrofuran, Kukhtin-Remirez adduct

引用此文

薛飞雪, 曾建伟, 严泰山, 韩杰, 贺峥杰. P(NMe₂)₃介导1,2-二羰基化合物与α,β-不饱和酮的[1＋4]环化反应及多取代2,3-二氢呋喃的合成[J]. 有机化学, 2022, 42(11): 3805-3815.

Feixue Xue, Jianwei Zeng, Taishan Yan, Jie Han, Zhengjie He. Synthesis of Polysubstituted 2,3-Dihydrofurans via P(NMe₂)₃- Mediated [1＋4] Annulation of 1,2-Dicarbonyl Compounds with α,β-Unsaturated Ketones[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3805-3815.

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图/表 7

Scheme 1. Phosphorus reagent-mediated [1＋4] annulation reactions of 1,2-dicarbonyls, leading to dihydrofurans.

Entry	PR₃	Solvent	Time/h	Yield^b/%
1	P(NMe₂)₃	CH₂Cl₂	36	43
2	PPh₃	CH₂Cl₂	36	Trace
3	P(OMe)₃	CH₂Cl₂	36	Trace
4	P(OEt)₃	CH₂Cl₂	36	Trace
5	P(NMe₂)₃	Ethanol	36	Trace
6	P(NMe₂)₃	THF	36	7
7	P(NMe₂)₃	Et₂O	36	41
8	P(NMe₂)₃	CHCl₃	36	23
9	P(NMe₂)₃	1,4-Dioxane	36	57
10	P(NMe₂)₃	CH₃CN	36	60
11	P(NMe₂)₃	Toluene	36	71
12	P(NMe₂)₃	Toluene	12	23
13	P(NMe₂)₃	Toluene	24	40
14	P(NMe₂)₃	Toluene	48	63

Table 1. Survey on the model reaction conditionsa

Table 2. [1＋4] annulation of 1,2-dicarbonyl compounds 1 and α,β-unsaturated ketones 2a

Table 3. [1＋2] annulations of 1,2-dicarbonyl compounds 1 andα,β-unsaturated ketones 2a

Scheme 2. Reaction of N-CH3 isatin 1n and ethyl 2-benzoyl- acrylate 2a

Scheme 3. A plausible mechanism for formation of compounds 3 and 4

Scheme 4. DFT calculations

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P(NMe₂)₃介导1,2-二羰基化合物与α,β-不饱和酮的[1＋4]环化反应及多取代2,3-二氢呋喃的合成

Synthesis of Polysubstituted 2,3-Dihydrofurans via P(NMe₂)₃- Mediated [1＋4] Annulation of 1,2-Dicarbonyl Compounds with α,β-Unsaturated Ketones

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